Amidothionophosphoric acid phenyl esters

ABSTRACT

AMIDOTHIONEPHOSPHORIC ACID PHENYL ESTERS OF THE GENERAL FORMULA   1-(R4-N(-R5)-P(=S)(-O-R)-O-),2-(R1-OOC-),R2,R3-BENZENE   IN WHICH R AND R1 EACH IS A LOWER ALKYL RADICAL, R2 IS A HALOGEN, LOWER ALKYL OR LOWER ALKYLMERCAPTO RADICAL, AND R3, R4 AND R5 EACH IS HYDROGEN OR LOWER ALKYL RADICAL, WHICH POSESS INSECTICIDAL AND ACARICIDAL PROPERTIES.

United States Patent Oflice Patented Apr. 30, 1974 US. Cl. 260-941 7 Claims ABSTRACT OF THE DISCLOSURE Amidothionophosphoric acid phenyl esters of the general formula in which R and R each is a lower alkyl radical, R is a halogen, lower alkyl or lower alkylmercapto radical, and R R and R each is hydrogen or a lower alkyl radical,

which possess insecticidal and acaricidal properties.

The present invention relates to and has for its objects the provision of particular new amidothionophosphoric acid phenyl esters, i.e. N-alkylamido-O-alkyl-O-(2 carbalkoxy-substituted phenyl)-thionophosphoric acid ester amides, which possess insecticidal and acaricidal properties, active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new way especially for combating pests, e.g. insects and acarids, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

In German patent specification 814,152 there are described, among other things, N,N-dimethylamido-O-ethyland bis(N,N-dimethyl)-amidophosphoryl-salicylic acid ethyl esters (Compounds A and B, respectively) which are obtainable by reaction of alkali metal salts of the salicylic acid esters with the appropriate disubstituted phosphoric acid monochlorides. .According to the information given in German patent specification 811,514, the aforesaid compounds are suitable for the active and passive control of sucking and biting insects and may therefore be used as pesticides.

Furthermore, 0,0 dialkylthionophosphoryl-salicylic acid esters and their insecticidal and toxic activity are described in R. L. Metcalf: Organic Insecticides, Interscience Publishers, New York, 1955.

The present invention provides, as new compounds, the amidothionophosphoric acid phenyl esters of the general formula in which R and R each is a lower alkyl radical,

R is a halogen, lower alkyl or lower alkylmercapto radical, and

R R and R each is hydrogen or a lower alkyl radical,

The present invention also provides a processfor the preparation of a compound of the General Formula I, in which an O-alkyl-O-(Z-carbalkoxy-phenyl)-thionophosphoric acid diester monohalide of the general formula RO\S a Hal R:

is reacted with a primary general formula or secondary amine of the in which formulae R, R3 R R R and R have the meanings stated above,

Hal is a halogen atom, preferably a chlorine or bromine atom.

It has been found that the compounds of the Formula I are distinguished by outstanding insecticidal and acaricidal properties, low toxicity to warm-blooded animals, as well as in some cases, extremely low phytotoxicity. They possess activity against biting, sucking and soilinha'biting insects and in this respect are distinctly superior to the above-mentioned compounds of the prior art having analogous formulae. Therefore, the compounds of this invention represent a genuine enrichment of the, art.

The course of the reaction is illustrated by the followmg equation:

\1: ang NH HH. Hal 7 R: R

(II) (III) R0 R R4\ P-O /N 00B Ra Br Preferably, R denotes an alkyl group with 14, especially 1-3 carbon atoms, namely methyl, ethyl or nor iso-propyl; R is an alkyl radical with 1-4, especially 2-4 carbon atoms, for example ethyl, nor isopropyl'or sec.- or tert.-butyl; R is a chlorine atom or an alkyl or alkylmercapto radical with, in either case, 1-3 carbon atoms, namely methyl, ethyl, nor isopropyl, methylmercapto, ethyhnercapto or nor isopropylmercapto; R is a hydrogen atom or an alkyl group with 1-3 carbon atoms, namely, methyl, ethyl or nor isopropyl; and R is an alkyl radical with 1-3 carbon atoms, for example, methyl, ethyl or isopropyl; and R is a hydrogen atom.

The O-alkyl-O-(2-carbalkoxyphenyl)-thionophosphoric acid diester monohalides of the Formula II, required as starting materials in the preparative process, have not hitherto been described in the literature. However, they are readily obtainable, even on an industrial scale, by reaction of O-alkyl-thionophosphoric acid ester dihalides with appropriate nuclear-substituted salicylic acid alkyl esters in the presence of solvents or diluents and of acidacceptors. Good results have been obtained with the use of alkali metal hydroxides, carbonates and alcoholates as acid-acceptors, such as sodium or potassium hydroxide, methylate or ethylate, as well as tertiary bases, such as triethylamine, diethylaniline, dimethylbenzylamine or pyridine. Furthermore, it is possible, instead of working in the presence of acid-binding agents, to start with suitable salts of the nuclear-substitued salicylic acid esters concerned, preferably the alkali metal or ammonium salts thereof.

It has proved expedient to add the O-alkyl-thionophosphoric acid ester dihalide to a mixture of the salicylic acid ester, acid-acceptor and solvent (or of the salicylic acid ester salt and solvent), but the reverse manner of addition may be chosen.

The reaction of the O-alkyl-O-(2-carbalkoxyphenyl)- thionophosphoric acid diester monohalide of the Formula II with the amine of the Formula III is preferably etfected in the presence of a solvent or diluent, for which purpose inert organic solvents may be used, especially aliphatic and aromatic optionally chlorinated hydrocarbons, such as methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, mono-, diand tri-chloroethylene, benzene, toluene, xylenes and chlorobenzene, and ethers, such as diethyl ether, dibutyl ether and dioxane.

The process of the present invention is preferably carried out with the use of an acid-binding agent. Although any of the acid-acceptors mentioned above may be used, it is expedient to employ an excess of the amine of the Formula III for this purpose.

The carrying out of the process is possible within a fairly wide temperature range. In general, the work is carried out at room temperature or slightly to moderately elevated temperatures and preferably at about 20 to 60 C. It has proved expedient to stir the reaction mixture, after combining the starting components, for a longer period, e.g. about 1 to 12 hours, possibly with slight heating, in order to complete the reaction.

According to the Equation IV stated above, theoretically there are required equimolar amounts of the starting materials. The working-up of the mixture may take place in any customary manner. For, example, when the reaction has been carried out in a water-immiscible solvent, for instance a hydrocarbon or ether, the working-up may be effected by washing the solution, evaporating the solvent after separation of the layers and drying of the organic phase, and, if possible, subjecting the residue to fractional distillation.

The amidothionophosphoric acid phenyl esters according to the present invention are, in most cases, colorless to slightly colored, water-insoluble oils which in most cases cannot, even under greatly reduced pressure, be distilled without decomposition. Such products can, however, by so-called slight distillation, that is brief heating to slightly to moderately elevated temperature, be freed from the last volatile constituents and in this Way be purified.

As already mentioned above, the amidothioniphosphoric acid phenyl esters according to the invention possess an outstanding, rapidly-occurring and long-lasting insecticidal and acaricidal activity with, in some cases, extremely low phytotoxicity. The products may therefore be used with success in crop protection for the control of noxious sucking and biting insects, Diptera and mites. To the sucking insects contemplated herein there belong,

in the main, aphids (Aphidae) such as the green peach aphid (Myzus persz'cae), the bean aphid (Doralz's fabae), the bird cherry aphid (Rhopalosiphum padi), the pea aphid (Macrosipham pisi) and the potato aphid (Macrosiphum solanz'foliz'), the currant gall aphid (Cryptomyzus korschelti), the rosy apple aphid (Sappaphis mall), the mealy plum aphid (Hyalopterus arundinis) and the cherry black-fly (Myzus cerasi); in addition, scales and mealybugs (Coccina), for example the oleander scale (Aspidiotus hederae) and the soft scale (Lecanium hesperidum) as well as the grape mealybug (Pseudococcus maritimus); thrips (Thysanoptera), such as Hercinothrips femoralis, and bugs, for example the beet bug (Piesma quadrata), the red cotton bug (Dysdercus intermedius), the bed bug (Cimex lectularius), the assassin bug (Rhodnius prolixus) and Chagas bug (T riatoma infestans) and, further, cicadas, such as Euscelis bilobatus and Nephotettix bipunctatus; and the like.

In the case of the biting insects contemplated herein, above all there should be mentioned butterfly caterpillars (Lepidoptera) such as the diamond-back moth (Plutella maculipennis), the gypsy moth (Lymantria dispar), the browntail moth (Euproctis chrysorrhoea) and tent caterpillar (Malwcosoma neustria); further, the cabbage moth (Mamestra brassicae) and the cutworm (Agroris segetum), the large white butterfly (Pieris brassicae), the small winter moth (Cheimatobia brumata), the green oak tortrix moth (Tortrix viridana), the fall arm-yworm (Laphygma frugiperda) and cotton worm (Prodenia litura), the ermine moth (Hyponomeuta padella), the Mediterranean flour moth (Ephestia kiZhniella) and greater wax moth (Galleria mellonella); and the like.

Also to be classed with the biting insects contemplated herein are bettles, (Coleoptera), for example the granary weevil (Sitophilus granarius=Calandra granaria), the Colorado bettle (Leptinotarsa decemlineata), the dock beetle (Gastrophysa viridula), the mustard bettle (Phaedon cochleariae), the blossom bettle (Meligethes aeneus), the raspberry bettle (Byturus lomentosus), the bean Weevil (Bruchidius=Acanthoscelia'es obtectus), the leather bettle (Dermestes frischi), the khapra beetle (Trogoderma granarium), the flour beetle (Tribolium castaneum), the northern corn billbug (Calandra or Sitaphilus zeamais) the drugstore bettle (Stegobium paniceum), the yellow mealworm (Tenebrio molitor) and the saw-toother grain bettle (Oryzaephilus surinamensis), and also species living in the soil, for example wiroworms (Agriotes spec.) and larvae of the cockchafer (Melolontha melolontha); cockroaches, such as the Germany cockroach (Blattella germanica), American cockroach (Periplaneta americana), Madeira cockroach (Leu ophaea or Rhyparobia maderae), oriental cockroach (Blazta orientalis), the giant cockroach (Blaberus giganteus) and the black giant cockroach (Blaberus fuscus) as well as Henschoutedenia flexivilta; further, Orthoptera, for example the house cricket (Acheta dom'esticu's); termites such as the eastern subterranean termite (Reticulz'termes flavipes) and Hymenoptera such as ants, for example the garden ant (Lasius niger); and the like.

The Diptera contemplated herein comprise essentially the files, such as the vinegar fly (Drosophila melanogaster), the Mediterranean fruit fly (Ceratitis capitata), the house fly (Musca domestica), the little house fly (Fannia canicularis), the black blow fly (Phormia regina) and bluebottle fly (Calliphora erythrocephala) as well as the stable fly (Stomoxys calcilrans); further, gnats, for example mosquitoes such as the yellow fever mosquito (Aedes aegypti), the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles stephensi) and the like.

With the mites (Acarina) contemplated herein there are classed, in particular, the spider mites (Tetranychi dae) such as the two spotted spider mite (Tetranychus telarius-Tetranychus althaeae or Tetranychus urticae) and the European red mite (Paratetranychus pilosus- Panonychus ulmi), gall mites, for example the black currant gall mite (Eriophyes ribis) and rarsonemids) for example the broad mite (H mi a svnemus l ws) and the cyclmen mite (Tarsonemus pallidus); finally, ticks, such as the relapsing fever tick (Ornithodorus moubata); and the like.

When applied against pests harmful to health and pests of stored products, especially flies and mosquitoes, the compounds are also distinguished by an outstanding residual activity on wood and clay, as well as a good stability to alkali on limed substrates.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/ or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as Freon; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), paraflins (e.g. petroleum fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, etc.), amines (e.g. ethanolamine, etc.), ethers, ether-alcohols (e.g. glycol monomethyl ether, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethylsulfoxide, etc.), ketones (e.g. acetone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, attapulgite, montomorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and/or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl arylpolyglyco ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite Waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other acaricides and insecticides, or fungicides, bactericides and nematocides, rodenticides, herbicides, fertilizers, growth-regulating agents, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concern commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 0.1-95 by weight, and preferably 05-90% by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0005-20%, preferably 0.005-5%, by

weight of the mixture. Thus, the present invention contemplates over-all compositions which comprise mixtures of a conventional dispersible carrier vehicle such as (1) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surfaceactive agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.0005-%, and preferably 0.01-95%, by weight of the mixture.

The active compounds can also be used in accordance with the well known ultra low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e.g. average particle diameter of from 50 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 15 to 1000 g./hectare, preferably 40 to 600 g./hectare, are sufiicient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about 95% by weight of the active compound or even the 100% active substance alone, e.g. about 20-100% by weight of the active compound.

Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. insects and acarids, which comprises applying to at least one of correspondingly (a) such insects, (b) such acarids, and (c) the corresponding habitat thereof, i.e. the locus to be protected a correspondingly combative or toxic amount, i.e. an insecticidally or acaricidally effective amount, of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, fumigating, and the like.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particular new compounds of the present invention are illustrated, without limitation, by the following examples.

EXAMPLE 1 Phaedon larvae test Solvent: 3 parts by weight acetone. Emulsifier: 1 part by weight alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier, and the concentrate is diuted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation of the active compound until dripping wet and then infested with mustard beetle larvae (Phaedon cochleariae).

After the specified periods of time, the degree of destruction is determined as a percentage: 100% means that all the beetle larvae are killed. 0% means that none of the beetle larvae are killed.

The active compounds, the concentration of the active compound, the times of evaluation and the results can be seen from the following Table 1.

TABLE 1 (Phaedon larvae test) Concentration Degree of I of active destruction compound in percent Active compound (constitution) in percent after 3 days (CzH50)zP-O (3-0 02115 (known) (A) CQHBO 0 o 0.1 100 \{1 ll 0.01 0 -0 OCgH (CHa)aN (known) (B) (GH:)aN\ (I? 0.1 0

' -o 'c-oczm (CHflzN (known) (1) 021150 5 O 0.1 100 \H II 0.01 100 /PO ()-OCH(CHa)2 0.001 95 CHr-NH (2) 031150 S 0 CH; 0.1 100 1| I 0.01 100 P-O -OC GE's-NH (32 (3) C2Ha0 S O 0.1 100 7 \II [1 0.01 100 /PO 0 C211: 0.001 100 (CHahCH-NH (4) CzHaO S O 0.1 100 \H II 0.01 100 P-O C-O CH(CHz)z 0.001 100 0.0001 100 (CHa):CH-NH C2H50\Si (H) /CH| 006i -o (3-0 CH 0.001 80 (CHa):CH-NH 08H! CHzO S O 0.1 100 \ll 1] 0.01 100 P-O -0 amon I 0.001 75 CHuN 7).::.:..::::: CH;O S O 0.1 100 \[I (I; 0.01 100 P-O O CH(CH|): 0.001 100 0.0001 90 cHmoH-NH EXAMPLE '2 To produce a suitable preparation of active compound,

Plutena test 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount Solvent: 3 parts by weight acetone of emulsifier and the concentrate is diluted, with water to Emulnfist; 1 p t y w geh a y yl p yg y ol ether. 76 the desi ed concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation of the active compound until dew moist and are then infested with caterpillars of the diamondback moth (Plutella maculipennis).

After the specified periods of time, the degree of destruction is determined as a percentage: 100% means that all the caterpillars are killed whereas 0% means that none of the caterpillars are killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from Table 2.

TABLE 2 (Plutella test) Concentration Degree 0! active destruction compound in percent Active compound (constitution) in percent after 3 days (C) S O 0.1 80 ll 0.01 0 (CzH;O)gP-O OC2H .(known) O OCaHs 3 (known) (B) (CH3)2N O O 0.1 0

\J I ll 0 C-OC H;

(8) CzH O S O 0.1 100 \H 0.01 /P-O -OC2H5 CHaNH Q (1).; CzHgO S O 0.1 100 \H II 0.01 100 /P-O C-OCH(CH1)2 0.001 CHa-NH Q 1 2 C H O S O CH 0.1 100 U a a 0.01 so -O OCH CHx-NH Q $1115 C O S O 0.1 100 \n n 0.01 100 /PO C-O 01H; 0. 001 (CHa)2CH-NH Q C H O O 0.1 (4 a 1 0.01 100 O COCH(CH3): 0.001 100 (CHa)2CH-NH Q 5 C H O S O CH 0.1 100 \n I 0.01 00 /PO OCH (CHa):CH-NH 272B;

1 1 1 2 4 TABLE 2Continued Concentration Degree oi 01 active destruction compound in percent Active compound (constitution) in percent after 3 days (6) CHzO S 0.1 100 \i! ll 0.01 100 /PO COCH(CH:): CHs-NH (7)-;3333333 CHsO S O 0.1 100 \H II 0.01 100 P-O C--OCH(CHa): 0.001 70 (CH3):CHN Q EXAMPLE 3 EXAMPLE 4 Myzus test (contact action) Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylarylpolyglycol ether.

To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Cabbage plants (Brassica oleracea) which have been heavily infested with peach aphids (Myzws persicae) are sprayed with the preparation of the active compound until dripping wet.

After the specified periods of time, the degree of destruction is determined as a percentage: 100% means that all the aphids are killed whereas 0% means that none of the aphids are killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table 3.

TABLE 3 (Myzus test) Tetranychus test Solvent: 3 parts by Weight acetone Emulsifier: 1 part by weight alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate so obtained is diluted with water to the desired concentration.

Beanplants (Phaseolus vulgaris), which have a height of approximately 10-30 cm., are sprayed with the preparation of the active compound until dripping wet. These bean plants are heavily infested with spider mites (T etranychus urticae) in all stages of development.

After the specified periods of time, the elfectiveness of the preparation of active compound is determined by counting the dead mites. The degree of destruction thus obtained is expressed as a percentage: 100% means that all the spider mites are killed whereas 0% means that none of the spider mites are killed.

Active compound (constitution) (GHa)aCH-NH Concentration Degree of of active destruction compound in percent in percent after 1 day The active compounds, the concentrations of the active compound is intimately mixed with soil. The concentracompounds, the evaluation times and the results can be tion vof the active compound in the preparation is of seen from the following Table 4. practically no importance; only the amount of active com- TABLE 4 (Tetranychus test) n Degree of Concentration destruction in of active percent after compound Active compound (constitution) in percent 8 days 2 days (B) (CH3)2N\ 0 0.1 0 nun...

(1)--..'..'.-:.'.-. C3H50\ S o 0.1 98 "1"...

/O -QCHGJH)! CHr-NH Q O OH CH NH Q 02 (3) "I"... 21 s 0 0. I. 0. 01 1 O -O 03H (CHI)2CHNH Q (4)..::....:-.-: CZHIO s o 0. I 98 (CHa)aCH-NH Q EXAMPLE 5 pound per unit volume of soil, which is given in ppm. (for example mg./l.), is decisive. The soil is filled into Cntlcal concentratlon test/511 Insects pots and the pots are left to stand at room temperature.

t: abba e root fl ma ots Phorbia brassicae After 24 hours, the test animals are put into the treated 325; s g i soil and, after a further 48 hours, the degree of effec tiveness of the active compound is determined as a per- Emulslfier' 1 Part by weight alkylarylpolyglycol ether. centage by counting the dead and living test insects. TO produce a suitable preparation Of active compound, The degree of destruction is 100% when all the test in- 1 part by weight of active compound is mixed with the sects have been killed; it is 0% when exactly as many stated amount of solvent, the stated amount of emulsitest insects are still alive as in the case of the control. fier-is' added and the concentrate is diluted with water The active compounds, the amounts applied and the to the desired concentration. The preparation of active results can be seen from the following Tabl'eSJ Active compound (constitution) Concentration of active compound in p.p.m.

Degree of destruction jn percent (3) (hH O E (II) 100 100 100 95 90 P-O C C3H5 (CHa):CH-NH Q (4)--:-:::..;..: CaH50\fi 100 100 100 90 20 /P() C-OCH(CH3)I (CHahCH-NH Q (1)..;-;.'..'.'.-...- C HO\fi (III) 100 100 100 75 /P-O C-OCH(CH8): CHg-NH 5 F l (5) 5.1.1.; CzH50\S CH: 100 100 70 7:21:27";

-0 C OCH (CH3):CH-NH Cal-Ii (2) C H5O CH; 100 100 70 r-o o-o-on CHx-NH 03H CH; C]

C'O--CH (C) .:'.'..2::::':.-. 0 l] g (hHgOhP-o 0 C211;

(Known) 2 13: (CHDzN 0 0 :.::r;-r..-=::..;.

P-O C-OCgHs HMN (known) (A)-:::=::::: CaHsO 0 (CH:)|N

(known) EXAMPLE 6 To produce a suitable preparation of active com- Critical concentration test/soil insects Test insect: Agriotes sp.

Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylarylpolyglycol ether.

pound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration. The preparation of active compound is intimately mixed with soil. The con- 17 centration of the active compound in the preparation is of practically no importance; only the amount of active compound per unit volume of soil, which is given in p.p.m. (for example mg./l.), is decisive. The soil is filled into pots and the pots are left to stand at room tempera- 18 solved in 300 cc. of benzene. To this solution there are added at room temperature, with stirring, 30 g. of methylamine dissolved in 150 cc. of benzene. The mixture is subsequently stirred for 2 hours and washed twice, in each case with 100 cc. of water. The benzene solution ture. After 24 hours, the test animals are put into the is separated and the latter is dried over sodium sulfate. treated soil and, after a further 48 hours, the degree of After the solvent has been distilled oil, 108 g. (88% of effectiveness of the active compound is determined as a theory) of N-methylamidothionophosphoric acid O-ethylpercentage by counting the dead and living test insects. O-(Z-carbisopropoxy-4-chlorophenyl) ester are obtained The degree of destruction is 100% when all the test inin the form of a colorless, water-insoluble oil with a sects have been killed; it is 0% when exactly as many test refractive index m, of 1.5360. insects are still alive as in the case of the control. Calculated for a molecular weight of 351.5 (percent): The active compounds, the amounts applied and the P, 8.8; S, 9.1; N, 3.98; CI, 10.1. Found (percent): P, 8.7; results can be seen from the following Table 6. S, 9.0; N, 3.7; CI, 10.3.

TABLE 6 (Agriotes sp. in the soil) Concentration of active compound in p.p.m.

Degree of destruction in Active compound (constitution) percent (a) CEH50\S 0 100 100 100 95 /i -O i l-00 E; (CH3)zCH-NH (4 02H0 S 100 100 95 so l 4% O -OCH(CH8)2 (CH3)2CHNH Q 61 1 CZHEO s 0 100 100 l l --O -OCIEKCHQI CHa-NH l ll (021150): 0 l-OCgH5 (B) (CHaMN S 0 0 1 O -OCaH; (CHIOZN Q (known) (A) C2H5O\fi 0 P-O A l-002E; (CH3)2N Q (known) The preparative process is illustrated in and by the EXAMPLE 8 following examples.

EXAMPLE 7 65 fi' 3 5 0 H 0 S /PO -0-C\ 2 5 H g CHJ-NH cm,

/PO -OCH(CH;)1 CHa-NH .51 (2) 0.35 molar mixture.

0.35 molar mixture.

g. of O-ethyl-O-(2-carbisopropoxy-4-chl0rophenyl)-thionophosphoric acid diester-monochloride are dis- 'To a solution of g. of O-ethyl-O-(2-carb-sec.-butoxy 4 chlorophenyl)-thi0nophosphoric acid diester monochloride in 300 cc. of benzene there are added, with stirring, 30 g. of methylamine dissolved in cc. of

0.42 molar mixture.

152 g. of O-ethyl-O-(2-carbethoxy-4-chlorophenyl)- thionophosphoric acid diester monochloride are dissolved in 400 cc. of benzene. To this solution there are added at room temperature, with stirring, 51 g. of isopropylamine in 100 cc. of benzene. The mixture is afterwards stirred for 12 hours and then worked up as in Example 7. There are obtained 148 g. (97% of theory) of N-isopropylamidothionophosphoric acid O-ethyl-O-(Z-carbethoxy-4-chlorophenyl)-ester in the form of a colorless, water-insoluble oil with a refractive index n of 1.5327.

Calculated for a molecular weight of 365.5 (percent): P, 8.48; S, 8.77; N, 3.8; Cl, 9.73. Found (percent): P, 8.1; S, 8.5; N, 3.6; CI, 10.0.

EXAMPLE 10 (CH3); C H-N 0.4 molar mixture.

143 g. of O-ethyl-O-(2-carbisopropoxy-4-chlorophenyl)-thionophosphoric acid diester monochloride are dissolved in 500 cc. of benzene; to this solution there are added at room temperature, With stirring, 53 g. of isopropylamine in 100 cc. of benzene; the mixture is subsequently stirred for 2 hours and then worked up as in Example 7. There are so obtained 128 g. (85% of theory) of N-isopropylamidothionophosphoric acid O-ethyl-O-(2- carbisopropoxy-4-chlorophenyl)-ester as a water-insoluble, colorless oil with a refractive index n of 1.5262.

Calculated for a molecular weight of 375.5 (percent): P, 8.27; S, 8.5; N, 3.7; CI, 9.46. Found (percent): P, 8.1; S, 8.3; N, 3.5; Cl, 9.9.

EXAMPLE 11 031150 S 0 CH3 85 (CHmCH-NH C2115 20 Calculated for a molecular weight of 393.5 (percent): P, 8.08; S, 8.1; N, 3.56; Cl, 9.03. Found (percent): P, 8.1; S, 7.9; N, 3.4; Cl, 9.4.

EXAMPLE 12 S Ol O CH:

N H CaHviSO Ha I From 117 g. of O-methyl-O-(2-carbisopropoxy-3,5-dimethylphenyl)-thionophosphoric acid diester monochloride and 45 g. of isopropylamine there are obtained in a manner analogous to the foregoing examples g. (76% of theory) of N-isopropylamidothionophosphoric acid 0- methyl-O- (2-carbisopropoxy-3,S-dimethylphenyl) ester as a colorless, water-insoluble oil with a. refractive index n of 1.5180.

EXAMPLE 13 E30 i -OPOCH:

Ha (I) NH- CzH5 0 C3H71SO 117 g. of O-methyl-O-(2-carbisopropoxy-3,S-dimethylphenyl)-thionophosphoric acid diester monochloride and 50 g. of a 50% strength aqueous ethylamine solution yield 91 g. (75% of theory) of N-ethylamidothionophosphoric acid O methyl-O-(2-carbisopropoxy-3,5-dimethylphenyl ester as a colorless, water-insoluble oil with a refractive index 11 of 1.5217.

EXAMPLE l4 C H O S O pJ-OCHKlI-Ig): GHQ-NH. I

CHa By reaction of 63 g. of O-ethyl-O-(Z-carbisopropoxy- 4 methylmercaptophenyl)-thionophosphoric acid diester monochloride with 14 g. of methylamine dissolved in cc. of benzene, there are obtained 50 g. (79% of theory) of N-methylamidothionophosphoric acid O-ethyl O (2- carbisopropoxy 4 methylmercaptophenyl)-ester as a colorless, water-insoluble oil with a refractive index n;, of 1.5607.

EXAMPLE 15 CH3S O-E-O 02H5 (CH3)Z I -O CaHviSO EXAMPLE 16 CH 3 Z CHJNH From 51 g'. of O-ethyl-O-(2-carbisopropoxy-4-methyl-' By reaction of 105 g. of O-methyl-O-(2-carbisopropoxy- 4-chlorophenyl)-thionophosphoric acid diester monochloride with 20 g. of methylamine dissolved in 100 cc. of benzene, there are obtained 35 g. of N-methylamidothionophosphoric acid O-methyl-O-( 2 carbisopropoxy-4- chlorophenyl) ester as a colorless, water-insoluble oil with a refractive index mi of 1.5449.

105 g. of O-methyl-O-(Z-carbisopropoxy-4-chlorophenyl)-thionophosphoric acid diester monochloride and 38 g. of isopropylamine yield 77 g. (76% of theory) of N-isopropylamidothionophosphoric acid O-methyl-O-(Z- carbisopropoxy 4 chlorophenyl)-ester as a colorless, water-insoluble oil with a refractive index u of 1.5330.

EXAMPLE 18 From 105 g. of O-methyl-O-(2-carbisopropoxy-4-chlorophenyl)-thionophosphoric acid diester monochloride and 30 g. of dimethylamine dissolved in 100 cc. of henzene, there are obtained 75 g. (71% of theory) of N,N- dimethylamidothionophosphoric acid O-methyl O (2- carbisopropoxy-4-chlorophenyl)-ester with a refractive index n;, of 1.5380.

It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention.

What is claimed is:

1. Amidothionophosphoric acid phenyl esters of the general formula R S R: r x- 00 R] R: Rs

in which R and R each is a lower alkyl radical.

R is a halogen, lower alkyl or lower alkylmercapto radical,

R and R each is hydrogen or a lower alkyl radical,

R and R when other than hydrogen, being located in the 3-, 4- or S-position, and

R is a lower alkyl radical.

2. Compounds according to claim 1, in which R is an alkyl radical with l-3 carbon atoms; R, is an alkyl radical with 2-4 carbon atoms, R is a chlorine atom or a methyl or methylmercapto radical; R is a hydrogen atom or 22 a methyl radical; R is an alkyl radical with l-3 carbon atoms; and R is a hydrogen atom.

- 3. Compound according to claim 1 wherein such compound is N-methylamidothionophosphoric acid O-ethyl- O-(Z-carbisopropoxy-4-ch1orophenyl)-ester of the formula CHr-N o 8-0 cmom),

4. Compound according to claim 1 wherein such compound is N-methylamidothionophosphoric acid O-ethyl- 0-(Z-carb. sec.-butoxyphenyl)-ester of the formula C Ha-N (51 5. Compound according to claim 1 wherein such compound is N-isopropylamidothionophosphoric acid O-ethyl- 0-(2-carbethoxy-4-chlorophenyl)-ester of the formula CIH5O\ S P- (CH:)2CH--Nfi 0 8-0 CRHB References Cited UNITED STATES PATENTS 3,621,082 11/ 1971 Schrader et al 260-941 3,351,682 11/ 1967 Baker et al 260-941 X ANTON H. SUTTO, Primary Examiner v es 4 r n m a e e I: ,k

' CERHFIMAML m CORRECHQN 22mm New 3% bated .April 30, 1974 xmwnmm clam-a mu) SCHRADER ETAL' fit is certified that verr-0r appearein the aboye-idcncified patent and that: said Letters Pamentarehereby corrected as shown below:

, I I I. ,7 I I I a 3 C01; n line 57, Ch E'iZgQ filQfS tD flies "Col. 5, line 53 change "a rylpolygjlyco" t0 f etylpelyglycol -.v C010 9; 710 Table 2', compound (4) cortect fof m ulato read as follows:

clmo s 0 .\n n v P-O C0CH(CIII):

"C01, 15 Table 5 Compound (A), before insert Signed end sealed this 22nd day of October 1974.v

' (SEAL) :Attestr v 4 MCCOY Mn GIBSON JR, C. MARSHALL DANN Atteeting Officer 7 Commissioner of Patents 

